EP0148344B1 - Utilisation de compositions formant des polyuréthanes comme matériaux de moulage - Google Patents

Utilisation de compositions formant des polyuréthanes comme matériaux de moulage Download PDF

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Publication number
EP0148344B1
EP0148344B1 EP84113000A EP84113000A EP0148344B1 EP 0148344 B1 EP0148344 B1 EP 0148344B1 EP 84113000 A EP84113000 A EP 84113000A EP 84113000 A EP84113000 A EP 84113000A EP 0148344 B1 EP0148344 B1 EP 0148344B1
Authority
EP
European Patent Office
Prior art keywords
groups
weight
epoxide
hydroxyl groups
epoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84113000A
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German (de)
English (en)
Other versions
EP0148344A1 (fr
Inventor
Heinrich Dipl.-Ing. Heine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT84113000T priority Critical patent/ATE30328T1/de
Publication of EP0148344A1 publication Critical patent/EP0148344A1/fr
Application granted granted Critical
Publication of EP0148344B1 publication Critical patent/EP0148344B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/58—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds

Definitions

  • the invention relates to the use of reaction mixtures which react to give polyurethanes with improved heat aging behavior and which essentially consist of organic polyisocyanates, organic polyether polyols and epoxy compounds as casting compounds.
  • Polyurethane plastics produced by the reaction of organic polyisocyanates with organic polyhydroxyl compounds have become firmly established in many areas of application. In some of these areas such as. B. as casting resin or in mold making in electrical engineering, in the field of adhesives or as paint or coating materials, it cannot be excluded that the polyurethanes will be exposed to higher temperatures for long periods. The long-term heat resistance of the polyurethanes is therefore an important property in terms of application technology. Casting resins or casting compounds based on polyurethane cannot generally be kept at temperatures above 120 ° C. for a prolonged period, since otherwise the dimensional stability of the plastics is no longer guaranteed (bubble formation) and the mechanical properties are adversely affected.
  • reaction mixtures of organic polyisocyanates, organic polyether polyols and a certain amount of epoxy compounds which react to give polyurethane were used according to the invention.
  • compositions containing polyurethane-forming reaction components which contain 10-50% of low molecular weight, polyhydric alcohols and 0.1 to 10 Contain% by weight of an uncured epoxy resin, deformed and cured.
  • the reaction mixtures of this prior publication are preferably carried out at elevated temperatures and are used in particular for the production of reinforced molded articles with increased heat resistance.
  • casting compositions are used according to the invention which do not contain low molecular weight polyols and which can be processed at 10-60 ° C. using the methods of casting resin technology to give polyurethane plastics with improved heat aging behavior.
  • Polyisocyanates suitable for the use according to the invention are any organic compounds which are usually used in polyurethane chemistry and have at least two isocyanate groups.
  • 4,4'-diisocyanatodiphenylmethane or industrial mixtures with 2,4'- and optionally 2,2'-diisocyanatodiphenylmethane, polyisocyanate mixtures of the diphenylmethane series, such as are obtained by phosgenation of aniline / formaldehyde condensates in a manner known per se are particularly suitable , and which contain varying amounts of higher homologues in addition to the diisocyanates mentioned, 2,4-diisocyanatotoluene and its technical mixtures with up to 35% by weight, based on the total mixture of 2,6-diisocyanatotoluene, hexamethylene diisocyanate, 1-isocyanate 3,3,5-trimethyl-5-isocyanatomethylcyclohexane
  • Polyether polyols suitable for the use according to the invention are those with at least two, preferably two to three alcoholically bound hydroxyl groups in the molecular weight range 400-6,000, preferably 1,000-4,000.
  • Suitable polyether polyols are the known alkoxylation products of suitable starter molecules such.
  • B water, ethylene glycol, propylene glycol, trimethylolpropane, glycerol, sorbitol, sucrose or any mixtures of such starter molecules using ethylene oxide and / or propylene oxide as alkoxylating agent.
  • Epoxides suitable for the use according to the invention are any organic compounds which have at least one epoxy group and which are practically free of hydroxyl groups, i.e. H. have a hydroxyl group content of at most 2.5% by weight, preferably at most 1% by weight. Glycidyl esters or ethers known per se from epoxy chemistry are particularly preferred. These compounds can have either one or more epoxy groups per molecule. Their epoxy equivalent weight is within the range from 100 to 300.
  • Typical examples of such epoxy compounds are phenyl and cresyl glycidyl ether with an epoxy equivalent weight from 140 to 160, butyl glycidyl ether with an epoxide equivalent weight from 154 to 172, polyepoxide compounds such as diglycidyl ether of bisphenol A with an epoxy equivalent weight of 170 to 300, o-rhthalic acid diglycidyl ester with an epoxy equivalent weight of less than 200, m- and p-phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl equivalent of the above-mentioned epoxy range from 100% of the other epoxide range of the above-mentioned further epoxide range the compounds mentioned by way of example in DE-OS-2438205, pages 4-6, containing compounds containing epoxy, insofar as they correspond to the above-mentioned conditions with regard to the hydroxyl group content
  • any auxiliaries and additives can be used in the use according to the invention.
  • these include, for example, dyes, plasticizers, fillers such as. As quartz powder, aluminum hydroxide or chalk, reinforcing materials such as glass fibers; Catalysts such as B. tert. Amines such as triethylenediamine or dimethylbenzylamine or on an organometallic basis such. B. tin (II) octoate or dibutyltin dilaurate; water-absorbing additives such as B. zeolites; Flame retardants such as B. the organophosphorus compounds used for this purpose in polyurethane chemistry; Propellants such as B. water or halogenated hydrocarbons such. B. trifluorochloromethane or difluorodichloromethane; Silicone-based foam stabilizers or leveling agents of the type known from coating technology.
  • the polyisocyanates a) and the polyether polyols b) are present in amounts which correspond to an equivalent ratio between isocyanate groups and hydroxyl groups of 0.7: 1 to 1.3: 1, preferably 1: to 1.25: . It is particularly preferred to use equivalent or slightly excess amounts of polyisocyanates, based on the polyhydroxyl compounds.
  • at least one epoxy compound of the type mentioned by way of example is incorporated into the reaction mixture or before mixing the two main components of at least one of the individual components.
  • the epoxy compound or epoxy compounds are generally used in an amount such that 0.1 to 1, preferably 0.1 to 0.75, epoxy groups are present in each isocyanate group of the polyisocyanate component.
  • auxiliaries and additives which are optionally to be used are generally admixed with the polyol component, although their mixing with the polyisocyanate component can in principle also be considered.
  • the reactants and the auxiliaries and additives can be mixed by all customary methods of the prior art.
  • the casting compounds to be used according to the invention react within the temperature range of 10-60 ° C. to give polyurethane plastics, ie. H. especially molded polyurethane parts with an improved heat aging behavior.
  • 100 parts of a polyether polyol made of trimethylolpropane and propylene oxide with a viscosity of 600 ⁇ 100 mPa.s at 25 ° C and an OH content of approx. 11.3% are mixed with 10 parts of a paste of 50% of a zeolite powder and 50% Castor oil and mixed with 40 parts of a liquid epoxy resin made of bisphenol A and epichlorohydrin with a viscosity of approx. 10,000 mPa.s at 25 ° C, an epoxy equivalent weight of 195 and an OH content of 0.2%. This mass is degassed in a vacuum of approx. 0.5 mbar with stirring.
  • the hardened hard molding material is cut into standard bars measuring 150 x 10 x 15 mm. These rods are stored in a drying oven at 180 ° C. After 30 and 48 days, the test rods are removed and examined. It is shown that the molded materials are darker on the surface than the starting material due to the heat aging, but that the shape is still completely intact after 30 days and that only slight deformations can be determined after 48 days of storage at 180 ° C. When cutting the test specimens, the cast resin molding material is still compact without any gas inclusions.
  • Standard rods are produced in the same way from the same components as described in Example 1 without the addition of epoxy resin.
  • the test specimens When stored at 180 ° C in a drying oven, the test specimens are already clearly deformed after 30 days. After 48 days of storage, the originally rectangular rods have been transformed into round rods, and a clear foam structure can be seen when sliced open.
  • Test specimens for heat storage are produced from the starting materials and additives mentioned in Example 1, but with the addition of 0.2 part of dimethylbenzylamine as an accelerator for the polyurethane formation reaction.
  • the pot life of the mixture is 12 minutes compared to 60 minutes for the non-catalyzed mixture. It takes 8 hours at room temperature to harden the cast resin compound.
  • 500 parts of a polyether polyol based on trimethylolpropane and propylene oxide with a viscosity of approx. 800 mPa.s at 25 ° C and an OH content of approx. 1.05% are mixed with 50 parts of a paste of 50% zeolite powder and 50 % Castor oil, 2.5 parts of dimethylbenzylamine and 625 parts of a finely ground aluminum hydroxide powder. Then the mixture is divided into 5 equal portions. The first portion 2.5, the next 5.0, the third 7.5, the fourth 10.0 parts of the liquid epoxy resin according to Example 1 are mixed. The fifth subset is processed without the addition of epoxy resin.
  • the masses are then degassed in vacuo at 0.5 mbar with stirring and then mixed thoroughly with in each case 12.7 parts of the polyisocyanate according to Example 1.
  • the NCO / OH equivalent ratio is approx. 1.2: 1 in each case.
  • the equivalent ratio of epoxy to isocyanate groups is 0.14: 1, 0.28: 1, 0.41: 1, 0.55: 1 and 0: 1 (comparison).
  • the resin compositions thus produced have a pot life of approx. 15 min at room temperature.
  • test specimens For the production of test specimens, the masses are poured into sheet metal lids with a diameter of 100 m and a height of 6 mm. After 10 hours of storage at room temperature, elastic test specimens can be removed from the mold. First the Shore hardness A is determined at room temperature, then the test specimens are subjected to heat aging at 130 ° C in a heating furnace. To determine the aging behavior, the test specimens are removed from the oven at regular intervals, cooled to room temperature and the Shore hardness A measured again. The results are shown in the following table:
  • the test specimen without the addition of epoxy resin loses its hardness and strength much faster than the test specimen with the addition of epoxy resin.
  • Example 3 is repeated with the only difference that, instead of the epoxy resin based on bisphenol A, an epoxy resin of hexahydrophthalic acid and epichlorohydrin with a viscosity of 750 mPa.s / 25 ° C., an epoxy equivalent weight of 175 and an OH content of ⁇ 1% is used .
  • the results of the aging test (measured values of Shore hardness A) are summarized in the table below:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (2)

1. Utilisation de mélanges réactionnels comprenant :
a) des polyisocyanates organiques,
b) des polyéther-polyols comportant au moins deux groupes hydroxyle alcoolique et ayant un poids moléculaire se situant dans l'intervalle allant de 400 à 6 000,
c) au moins un composé époxy ayant une teneur maximale en groupes hydroxyle de 2,5 % en poids et un poids équivalent époxy de 100 à 300,
ainsi qu'éventuellement
d) des additifs et des agents auxiliaires connus en soi,

tout en maintenant un rapport équivalent de 0,7 : 1 à 1,3 : 1 entre les groupes isocyanate et les groupes hydroxyle, ainsi qu'un rapport équivalent de 0,1 : 1 à 1 : 1 entre les groupes époxy et les groupes isocyanate, comme matières de moulage réagissant à 10-60 °C pour former des matières synthétiques de polyuréthanes ayant un meilleur comportement au vieillissement thermique.
2. Utilisation selon la revendication 1, caractérisée en ce que, comme composant a), on utilise des produits de phosgénation de condensats d'aniline/formaldéhyde.
EP84113000A 1983-11-10 1984-10-29 Utilisation de compositions formant des polyuréthanes comme matériaux de moulage Expired EP0148344B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84113000T ATE30328T1 (de) 1983-11-10 1984-10-29 Verwendung von zu polyurethanenkunststoffen ausreagierenden reaktionsgemischen als giebmassen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3340588 1983-11-10
DE19833340588 DE3340588A1 (de) 1983-11-10 1983-11-10 Verfahren zur herstellung von polyurethanen mit einem verbesserten waermealterungsverhalten

Publications (2)

Publication Number Publication Date
EP0148344A1 EP0148344A1 (fr) 1985-07-17
EP0148344B1 true EP0148344B1 (fr) 1987-10-21

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ID=6213903

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Application Number Title Priority Date Filing Date
EP84113000A Expired EP0148344B1 (fr) 1983-11-10 1984-10-29 Utilisation de compositions formant des polyuréthanes comme matériaux de moulage

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EP (1) EP0148344B1 (fr)
AT (1) ATE30328T1 (fr)
DE (2) DE3340588A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4613660A (en) * 1985-02-19 1986-09-23 Ashland Oil, Inc. Polyol/polyepoxide/polyurethane adhesive
US4680346A (en) * 1985-12-13 1987-07-14 Ppg Industries, Inc. Flexible primer composition and method of providing a substrate with a flexible multilayer coating
US4870142A (en) * 1988-06-07 1989-09-26 Genesco Inc. Novel urethane polymer alloys with reactive epoxy functional groups
EP2885332B1 (fr) * 2012-08-20 2018-09-19 Covestro Deutschland AG Résines de coulée de polyuréthane et matériaux d'enrobage produits à partir de ces dernières

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3148167A (en) * 1958-11-14 1964-09-08 Gen Tire & Rubber Co Polyurethane composition containing an epoxy compound
BE696538A (fr) * 1966-07-13 1967-09-18
US3849349A (en) * 1971-05-12 1974-11-19 K Frisch Polyisocyanurate foam and process for producing the same
BE789670A (fr) * 1971-10-05 1973-04-04 Bayer Ag Procede de preparation d'objets moules en mousse
DE2331796A1 (de) * 1973-06-22 1975-01-16 Bayer Ag Hydrolyseschutzmittel fuer estergruppen enthaltende polyurethan-kunststoffe
DE2442434A1 (de) * 1974-09-05 1976-03-18 Hoechst Ag Pulverfoermiges ueberzugsmittel

Also Published As

Publication number Publication date
EP0148344A1 (fr) 1985-07-17
DE3340588A1 (de) 1985-05-23
DE3466882D1 (en) 1987-11-26
ATE30328T1 (de) 1987-11-15

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